WO2022158329A1 - Silica composite, resin composition, and resin film or resin sheet - Google Patents

Silica composite, resin composition, and resin film or resin sheet Download PDF

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Publication number
WO2022158329A1
WO2022158329A1 PCT/JP2022/000507 JP2022000507W WO2022158329A1 WO 2022158329 A1 WO2022158329 A1 WO 2022158329A1 JP 2022000507 W JP2022000507 W JP 2022000507W WO 2022158329 A1 WO2022158329 A1 WO 2022158329A1
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WIPO (PCT)
Prior art keywords
silica
silica composite
resin
composite
less
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PCT/JP2022/000507
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French (fr)
Japanese (ja)
Inventor
隆二 折井
昌司 林
Original Assignee
富士シリシア化学株式会社
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Filing date
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Application filed by 富士シリシア化学株式会社 filed Critical 富士シリシア化学株式会社
Priority to KR1020237028970A priority Critical patent/KR20230132863A/en
Priority to EP22742451.2A priority patent/EP4282822A4/en
Priority to US18/273,134 priority patent/US20240084108A1/en
Priority to CN202280011683.3A priority patent/CN116802150A/en
Publication of WO2022158329A1 publication Critical patent/WO2022158329A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/42—Gloss-reducing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the present disclosure relates to silica composites, resin compositions, and resin films or resin sheets.
  • Silica is used in a variety of applications, including as an additive in paints or inks, and as an anti-blocking agent for resin films or sheets.
  • silica is surface-treated with a specific compound for the purpose of imparting various properties to silica.
  • Patent Document 1 describes surface treatment of silica with wax in order to improve the precipitation behavior of silica in paint.
  • silica surface-treated with wax tends to associate in the resin composition and form aggregates. Therefore, for example, when silica is added as a matting agent for paints or inks, non-uniform unevenness is formed on the surface of the formed coating film or ink film, and there is a possibility that the surface will not be perfectly matted. There is Further, for example, when silica is added as an anti-blocking agent for a resin film or resin sheet, there is a possibility that fish eyes or the like due to aggregates may occur on the surface of the formed resin film or resin sheet. In this case, quality such as appearance and film strength deteriorates.
  • One aspect of the present disclosure is to provide silica that is uniformly dispersed in the resin composition. Moreover, one aspect of the present disclosure is to provide a resin composition and a resin film or resin sheet containing the silica.
  • One aspect of the present disclosure is a silica composite for a paint additive, an ink additive, or an anti-blocking agent for a resin film or resin sheet.
  • the silica composite has silica and a polyhydric alcohol bound or adsorbed to the silica.
  • the polyhydric alcohol may include a trihydric alcohol.
  • the polyhydric alcohol may contain at least one selected from the group consisting of glycerol, trimethylolethane, and trimethylolpropane.
  • the polyhydric alcohol may contain at least one selected from the group consisting of trimethylolethane and trimethylolpropane.
  • the content of the polyhydric alcohol in the silica composite may be 0.1% by mass or more and 30% by mass or less.
  • the ratio of the BET specific surface area obtained by the water vapor adsorption method to the BET specific surface area obtained by the nitrogen gas adsorption method may be 15% or more and 45% or less.
  • the silica composite may have a volume average particle size of 0.5 ⁇ m or more and 20 ⁇ m or less.
  • silica may include wet silica.
  • One aspect of the present disclosure is a resin composition containing the silica composite described above.
  • One aspect of the present disclosure is a resin film or resin sheet, which includes the silica composite for the anti-blocking agent of the resin film or resin sheet described above.
  • a silica composite for a paint additive, an ink additive, or an anti-blocking agent for a resin film or resin sheet wherein the silica composite comprises silica and A silica composite having bound or adsorbed at least one alcohol selected from the group consisting of monohydric alcohols and polyhydric alcohols and derivatives thereof may be provided.
  • silica is provided that is uniformly dispersed in the resin composition. Moreover, according to one aspect of the present disclosure, a resin composition and a resin film or resin sheet containing the silica are provided.
  • silica composite the resin composition, and the resin film or resin sheet according to one aspect of the present disclosure will be described in order.
  • the silica composite has silica and a polyhydric alcohol bound or adsorbed to the silica.
  • a silica composite can be suitably used as an additive for paint, an additive for ink, or an anti-blocking agent for resin films or resin sheets.
  • the silica composite may be a silica composite comprising silica and at least one alcohol selected from the group consisting of monohydric alcohols, polyhydric alcohols and derivatives thereof, bound or adsorbed to silica.
  • a silica composite can be obtained by surface-treating silica with the alcohols described above.
  • surface-treating silica with alcohols it is believed that the hydroxyl groups of the alcohols bond with the silanol groups on the silica surface, or the alcohols adsorb to the silica surface.
  • the alcohols referred to here may be understood as polyhydric alcohols. The same applies hereinafter.
  • hydrophobic groups such as alkyl groups derived from alcohols, hydroxyl groups derived from alcohols, and hydrophilic groups such as silanol groups on the silica surface are thought to be appropriately arranged.
  • Such a surface has a high affinity with paint, ink, or a resin component generally contained in a resin film or resin sheet, so that the silica composite is uniformly dispersed in the resin composition, and the silica composite Aggregation between bodies is suppressed.
  • the silica composite when added as a matting agent for paints or inks, uniform unevenness is formed on the surface of the formed coating film, and a smoothly matted surface with a good texture is obtained. be done.
  • the silica composite when added as a matting agent for the ink, a printed matter with high resolution can be obtained.
  • silica when silica is added as an anti-blocking agent for a resin film or resin sheet, fish eyes, unevenness, streaks and the like are less likely to occur in the resulting resin film or resin sheet.
  • the silica composite will be described in detail below.
  • porous silica is preferable because it is suitable for use as an additive for paints, an additive for ink, and an anti-blocking agent for resin films or resin sheets.
  • Porous silica includes wet silica produced by a wet method. Specific examples of wet silica include precipitated silica and silica gel.
  • silica gel is preferable because it is more suitable for use as an additive for paints, an additive for ink, and an anti-blocking agent for resin films or resin sheets.
  • alcohols include monohydric alcohols, polyhydric alcohols, and derivatives of polyhydric alcohols.
  • Examples of monohydric alcohols include monohydric saturated or unsaturated aliphatic alcohols, monohydric aromatic alcohols, and the like.
  • Examples of monohydric alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, s-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-methyl-1 -butanol, 1-hexanol, 2-hexanol, 2-ethyl-1-butanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, pinacolyl alcohol, benzyl alcohol, isopentenyl alcohol, 3 , 3-dimethylallyl alcohol, crotyl alcohol, ⁇ -methallyl alcohol, sorbyl alcohol and the like.
  • the number of carbon atoms in the monohydric alcohol is preferably
  • polyhydric alcohols include ethylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2 -dimethyl-1,3-propanediol, 1,2-hexanediol, 2-methyl-2,4-pentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, pinacol, diethylene glycol, triethylene glycol, tetra Ethylene glycol, propylene glycol, tripropylene glycol, glycerol, diglycerol, triglycerol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, sucrose and the like.
  • Polyhydric alcohols include, for example, compounds in which a portion of the hydroxyl groups of polyhydric alcohols are alkyl-etherified.
  • Examples of polyhydric alcohol derivatives include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, carbitol, and ethyl carbitol.
  • butyl carbitol triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono Ethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether and the like.
  • trihydric alcohol is preferable as the alcohol.
  • trihydric alcohols are considered to have more hydroxyl groups present on the surface of the silica composite without participating in bonding or adsorption with silica.
  • the balance between the hydrophobic groups and the hydrophilic groups present on the surface of the silica composite becomes appropriate, so that the silica composite is more uniformly dispersed in the resin composition.
  • the alcohol is preferably at least one selected from the group consisting of glycerol, trimethylolethane and trimethylolpropane, more preferably at least one selected from the group consisting of trimethylolethane and trimethylolpropane.
  • the content of the alcohol in the silica composite is preferably 0.1% by mass or more, more preferably 2% by mass or more, because the silica composite is more uniformly dispersed in the resin composition. preferable.
  • the content of alcohols in the silica composite is preferably 30% by mass or less, more preferably 15% by mass or less. preferable.
  • the ratio of the BET specific surface area obtained by the water vapor adsorption method to the BET specific surface area obtained by the nitrogen gas adsorption method is preferably 15% or more and 45% or less, and is 25% or more and 42% or less. is more preferably 25% or more and 40% or less.
  • the ratio is an index representing the degree of hydrophilicity/hydrophobicity of the substance to be measured, and the greater the value, the higher the hydrophilicity.
  • this ratio is referred to as "hydrophilic surface ratio”.
  • the greater the number of silanol groups, alcohol-derived hydroxyl groups, alcohol derivative-derived ether bonds, etc. on the silica surface the greater the value of the hydrophilic surface ratio.
  • the degree of hydrophilicity/hydrophobicity of the surface of the silica composite becomes appropriate, so that the silica composite is more uniformly dispersed in the resin composition.
  • the BET specific surface area determined by the nitrogen gas adsorption method is preferably 50 m/g or more and 800 m/g or less, more preferably 100 m/g or more and 550 m/g or less, and 200 m/g or more. It is more preferably 350 or less m ⁇ 2>/g.
  • a silica composite having a BET specific surface area within such a range is suitable for use as an additive for paints, an additive for inks, and an anti-blocking agent for resin films or resin sheets.
  • the pore volume of the silica composite is preferably 0.3 cm3/g or more and 2.2 cm3/g or less, more preferably 0.5 cm3/g or more and 2.0 cm3/g or less.
  • the pore volume referred to here is a value obtained by liquid-converting the amount of nitrogen gas adsorbed at a relative pressure of 0.99 on the nitrogen gas adsorption isotherm.
  • the average pore size of the silica composite is preferably 2 nm or more and 75 nm or less, more preferably 5 nm or more and 30 nm or less.
  • the average pore diameter can be calculated from the pore volume described above and the BET specific surface area determined by the nitrogen gas adsorption method described above.
  • the volume average particle size of the silica composite is preferably 0.5 ⁇ m or more and 20 ⁇ m or less, more preferably 1 ⁇ m or more and 15 ⁇ m or less, and even more preferably 2 ⁇ m or more and 8 ⁇ m or less.
  • the volume average particle diameter is within such a range, for example, irregularities of an appropriate size can be formed on the surface of a coating film, an ink film, or a resin film or resin sheet.
  • such silica having a relatively small volume-average particle size tends to aggregate, but aggregation can be suppressed by surface-treating the silica with the alcohols described above.
  • the volume average particle size referred to here is a value measured in an aqueous solution using a laser diffraction scattering particle size distribution analyzer.
  • a silica composite can be obtained by drying and pulverizing a pasty mixture obtained by mixing silica and a solution containing alcohols.
  • a predetermined amount of alcohol may be added in advance to the silica slurry liquid during the wet process, and the obtained mixed slurry liquid may be spray-dried to obtain the silica composite.
  • a slurry of silica obtained by a wet method and an alcohol may be mixed using a high-speed fluid mixer or the like, and the mixture may be dried and pulverized to obtain a silica composite.
  • the amount of alcohol used relative to silica is preferably 0.5 parts by mass or more, more preferably 2.0 parts by mass or more, relative to 100 parts by mass of silica.
  • the amount of alcohol used is 0.5 parts by mass or more with respect to 100 parts by mass of silica, the silica composite is more uniformly dispersed in the resin composition.
  • the amount of alcohol used relative to silica is preferably 12.0 parts by mass or less, more preferably 6.0 parts by mass or less, relative to 100 parts by mass of silica. This is because even if the amount of alcohol used is more than 12.0 parts by mass with respect to 100 parts by mass of silica, the effect of improving dispersibility is not so high.
  • the silica composite can be suitably used as a paint additive, an ink additive, or an anti-blocking agent for resin films or resin sheets.
  • Additives as used herein refer to all substances added to paints or inks for some purpose.
  • additives include matting agents and the like in the case of paints, and matting agents, pigments and the like in the case of inks.
  • the resin composition contains the silica composite described above.
  • resin compositions include paints, inks, compositions for forming resin films or resin sheets, and the like.
  • a composition for forming a resin film or a resin sheet refers to a raw material for forming a resin film or a resin sheet.
  • Examples of the shape of the resin composition include paste, pellet, plate, granule, and liquid.
  • the content of the silica composite in the resin composition can be appropriately set in consideration of the intended use of the silica composite, the physical properties required of the silica composite, and the like.
  • the content of the silica composite is preferably 0.5% by mass or more, more preferably 1% by mass or more.
  • the content of the silica composite is 0.5% by mass or more, desired physical properties, for example, when used as a matting agent, a desired degree of matting can be easily achieved.
  • the content of the silica composite is preferably 20% by mass or less, more preferably 15% by mass or less.
  • the content of the silica composite is preferably 50 ppm (0.005% by mass) or more, and is preferably 100 ppm (0.005% by mass) or more. 01% by mass) or more.
  • the content of the silica composite is 50 ppm or more, the effect as an anti-blocking agent is likely to be obtained.
  • the content of the silica composite is preferably 10,000 ppm (1% by mass) or less, more preferably 5,000 ppm (0.5% by mass) or less.
  • the silica composite is used to improve the surface properties of the resulting coating film, ink film, resin film or resin sheet, specifically, a matting agent for paints, a matting agent for inks, or It can be suitably used as an anti-blocking agent for resin films or resin sheets.
  • the paint, ink, or resin film or resin sheet may appropriately contain various components that are generally incorporated into the paint, ink, resin film, or resin sheet, in addition to the binder resin component.
  • resin components to be incorporated in paints or inks include acrylic resins, cellulose resins, urethane resins, alkyd resins, epoxy resins, melamine resins, and the like.
  • the resin component to be blended in the composition for forming the resin film or resin sheet include acrylic resin, nylon resin, PET resin, PP resin, PE resin, and the like.
  • the resin component to be blended in the composition for forming the resin film or resin sheet at least one selected from the group consisting of nylon resins, acrylic resins, and PET resins, since it has a high affinity with the silica composite. one is preferred.
  • the resin film or resin sheet contains the silica composite described above.
  • a resin film or resin sheet can be produced using the resin composition described above.
  • the resin film or resin sheet may be composed of a single layer, or may be composed of a plurality of layers including other layers.
  • Example 1 Preparation of Silica Composite A 1% by weight aqueous solution of trimethylolethane (TME) was prepared. 4 g of silica gel (“Silysia (registered trademark) 350” manufactured by Fuji Silysia Chemical Co., Ltd.) was added to 20 g of a 1% by mass trimethylolethane aqueous solution and mixed to obtain a paste-like mixture. The resulting mixture was dried in a dryer at 110 degrees. A silica/TME composite having a volume average particle size of 3.9 ⁇ m was obtained by pulverizing the resulting dried product.
  • TME trimethylolethane
  • Example 2 A silica/TME composite with a volume average particle size of 3.9 ⁇ m and a coating material were obtained in the same manner as in Example 1, except that the concentration of the trimethylolethane aqueous solution was 2% by mass.
  • Example 3 A silica/TME composite and a paint having a volume average particle size of 3.9 ⁇ m were obtained in the same manner as in Example 1, except that the concentration of the trimethylolethane aqueous solution was changed to 0.6% by mass.
  • Example 4 A silica/TMP composite with a volume average particle size of 3.9 ⁇ m and a paint were obtained in the same manner as in Example 1, except that trimethylolpropane (TMP) was used instead of trimethylolethane.
  • TMP trimethylolpropane
  • Example 5 A silica-glycerol composite with a volume average particle size of 3.9 ⁇ m and a paint were obtained in the same manner as in Example 1, except that glycerol was used instead of trimethylolethane.
  • Example 6 Same as Example 1 except that silica gel (“Silysia (registered trademark) 440”, manufactured by Fuji Silysia Chemical Co., Ltd.) was used instead of silica gel (“Silysia (registered trademark) 350”, manufactured by Fuji Silysia Chemical Co., Ltd.). Then, a silica/TME composite and a paint having a volume average particle size of 6.2 ⁇ m were obtained.
  • Example 4 A silica gel surface-treated with a silylating agent ("Sylophobic (registered trademark) 200", manufactured by Fuji Silysia Chemical Co., Ltd.) was prepared. The paint was prepared as in Example 1.
  • the ratio of the BET specific surface area obtained from the water vapor adsorption isotherm to the BET specific surface area obtained from the nitrogen gas adsorption isotherm was calculated.
  • A It has a smooth surface with uniform and fine unevenness.
  • Example 1 was superior to Example 3, and Example 2 was further superior in the smoothness of the coating film surface.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Compounds (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

Provided is a silica composite that disperses uniformly in a resin composition. This silica composite has silica and a polyvalent alcohol bonded or adsorbed to the silica, and is a silica composite for a coating additive, an ink additive, or an anti-blocking agent of a resin film or resin sheet.

Description

シリカ複合体、樹脂組成物、及び樹脂フィルム又は樹脂シートSilica composite, resin composition, and resin film or resin sheet 関連出願の相互参照Cross-reference to related applications
　本国際出願は、２０２１年１月２５日に日本国特許庁に出願された日本国特許出願第２０２１－００９５６２号に基づく優先権を主張するものであり、日本国特許出願第２０２１－００９５６２号の全内容を本国際出願に参照により援用する。 This international application claims priority based on Japanese Patent Application No. 2021-009562 filed with the Japan Patent Office on January 25, 2021, and Japanese Patent Application No. 2021-009562 The entire contents are incorporated by reference into this international application.
　本開示は、シリカ複合体、樹脂組成物、及び樹脂フィルム又は樹脂シートに関する。 The present disclosure relates to silica composites, resin compositions, and resin films or resin sheets.
　シリカは、塗料又はインクに配合される添加剤、樹脂フィルム又は樹脂シートのアンチブロッキング剤他、様々な用途に使用される。 Silica is used in a variety of applications, including as an additive in paints or inks, and as an anti-blocking agent for resin films or sheets.
　シリカに様々な特性を付与する目的で、シリカを特定の化合物で表面処理する場合がある。例えば、特許文献１には、塗料中でのシリカの沈殿挙動を改良するため、シリカをワックス（ロウ）で表面処理することが記載されている。 In some cases, silica is surface-treated with a specific compound for the purpose of imparting various properties to silica. For example, Patent Document 1 describes surface treatment of silica with wax in order to improve the precipitation behavior of silica in paint.
特公昭５１－３１２３５号公報Japanese Patent Publication No. 51-31235
　本発明者らの検討によれば、ワックスで表面処理されたシリカは、樹脂組成物中で会合し、凝集体を形成しやすい。そのため、例えばシリカが塗料又はインクの艶消し剤として添加される場合には、形成された塗膜又はインク膜の表面に不均一な凹凸が形成され、綺麗に艶消しされた表面にならない可能性がある。また、例えばシリカが樹脂フィルム又は樹脂シートの、アンチブロッキング剤として添加される場合には、形成された樹脂フィルム又は樹脂シートの表面に、凝集体に起因するフィッシュアイ等が生じる可能性がある。この場合、外観、フィルム強度等の品質が低下する。 According to the studies of the present inventors, silica surface-treated with wax tends to associate in the resin composition and form aggregates. Therefore, for example, when silica is added as a matting agent for paints or inks, non-uniform unevenness is formed on the surface of the formed coating film or ink film, and there is a possibility that the surface will not be perfectly matted. There is Further, for example, when silica is added as an anti-blocking agent for a resin film or resin sheet, there is a possibility that fish eyes or the like due to aggregates may occur on the surface of the formed resin film or resin sheet. In this case, quality such as appearance and film strength deteriorates.
　本開示の一局面は、樹脂組成物中に均一に分散されるシリカを提供することにある。また、本開示の一局面は、当該シリカを含む、樹脂組成物、及び樹脂フィルム又は樹脂シートを提供することにある。 One aspect of the present disclosure is to provide silica that is uniformly dispersed in the resin composition. Moreover, one aspect of the present disclosure is to provide a resin composition and a resin film or resin sheet containing the silica.
　本開示の一態様は、塗料の添加剤用、インクの添加剤用、又は、樹脂フィルム若しくは樹脂シートのアンチブロッキング剤用のシリカ複合体である。シリカ複合体は、シリカと、シリカに結合又は吸着した、多価アルコールと、を有する。 One aspect of the present disclosure is a silica composite for a paint additive, an ink additive, or an anti-blocking agent for a resin film or resin sheet. The silica composite has silica and a polyhydric alcohol bound or adsorbed to the silica.
　本開示の一態様では、多価アルコールは三価アルコールを含んでもよい。 In one aspect of the present disclosure, the polyhydric alcohol may include a trihydric alcohol.
　本開示の一態様では、多価アルコールは、グリセロール、トリメチロールエタン、及びトリメチロールプロパンからなる群より選ばれる少なくとも一つを含んでもよい。 In one aspect of the present disclosure, the polyhydric alcohol may contain at least one selected from the group consisting of glycerol, trimethylolethane, and trimethylolpropane.
　本開示の一態様では、多価アルコールは、トリメチロールエタン、及びトリメチロールプロパンからなる群より選ばれる少なくとも一つを含んでもよい。 In one aspect of the present disclosure, the polyhydric alcohol may contain at least one selected from the group consisting of trimethylolethane and trimethylolpropane.
　本開示の一態様では、シリカ複合体における多価アルコールの含有量が、０．１質量％以上３０質量％以下であってもよい。 In one aspect of the present disclosure, the content of the polyhydric alcohol in the silica composite may be 0.1% by mass or more and 30% by mass or less.
　本開示の一態様では、シリカ複合体において、窒素ガス吸着法により求められるＢＥＴ比表面積に対する、水蒸気吸着法により求められるＢＥＴ比表面積の割合が、１５％以上４５％以下であってもよい。 In one aspect of the present disclosure, in the silica composite, the ratio of the BET specific surface area obtained by the water vapor adsorption method to the BET specific surface area obtained by the nitrogen gas adsorption method may be 15% or more and 45% or less.
　本開示の一態様では、シリカ複合体の体積平均粒子径が、０．５μｍ以上２０μｍ以下であってもよい。 In one aspect of the present disclosure, the silica composite may have a volume average particle size of 0.5 μm or more and 20 μm or less.
　本開示の一態様では、シリカは湿式シリカを含んでもよい。 In one aspect of the present disclosure, silica may include wet silica.
　本開示の一態様は、樹脂組成物であって、上述したシリカ複合体を含む。 One aspect of the present disclosure is a resin composition containing the silica composite described above.
　本開示の一態様は、樹脂フィルム又は樹脂シートであって、上述した樹脂フィルム又は樹脂シートのアンチブロッキング剤用のシリカ複合体を含む。 One aspect of the present disclosure is a resin film or resin sheet, which includes the silica composite for the anti-blocking agent of the resin film or resin sheet described above.
　本開示の別の態様では、塗料の添加剤用、インクの添加剤用、又は、樹脂フィルム若しくは樹脂シートのアンチブロッキング剤用のシリカ複合体であって、シリカ複合体は、シリカと、シリカに結合又は吸着した、一価アルコール、並びに多価アルコール及びその誘導体からなる群より選ばれる少なくとも一つのアルコール類と、を有する、シリカ複合体が提供されてもよい。 In another aspect of the present disclosure, a silica composite for a paint additive, an ink additive, or an anti-blocking agent for a resin film or resin sheet, wherein the silica composite comprises silica and A silica composite having bound or adsorbed at least one alcohol selected from the group consisting of monohydric alcohols and polyhydric alcohols and derivatives thereof may be provided.
　本開示の一態様によれば、樹脂組成物中に均一に分散されるシリカが提供される。また、本開示の一態様によれば、当該シリカを含む、樹脂組成物、及び樹脂フィルム又は樹脂シートが提供される。 According to one aspect of the present disclosure, silica is provided that is uniformly dispersed in the resin composition. Moreover, according to one aspect of the present disclosure, a resin composition and a resin film or resin sheet containing the silica are provided.
　以下、本開示の一態様に係る、シリカ複合体、樹脂組成物、及び樹脂フィルム又は樹脂シートについて順に説明する。 Hereinafter, the silica composite, the resin composition, and the resin film or resin sheet according to one aspect of the present disclosure will be described in order.
　＜シリカ複合体＞
　シリカ複合体は、シリカと、シリカに結合又は吸着した、多価アルコールと、を有する。このようなシリカ複合体は、塗料の添加剤、インクの添加剤、又は、樹脂フィルム若しくは樹脂シートのアンチブロッキング剤として好適に使用することができる。シリカ複合体は、シリカと、シリカに結合又は吸着した、一価アルコール、並びに多価アルコール及びその誘導体からなる群より選ばれる少なくとも一つのアルコール類と、を有するシリカ複合体であってもよい。 <Silica composite>
The silica composite has silica and a polyhydric alcohol bound or adsorbed to the silica. Such a silica composite can be suitably used as an additive for paint, an additive for ink, or an anti-blocking agent for resin films or resin sheets. The silica composite may be a silica composite comprising silica and at least one alcohol selected from the group consisting of monohydric alcohols, polyhydric alcohols and derivatives thereof, bound or adsorbed to silica.
　シリカ複合体は、シリカを上述したアルコール類で表面処理することにより得ることができる。シリカをアルコール類で表面処理することにより、アルコール類の水酸基がシリカ表面のシラノール基と結合したり、アルコール類がシリカ表面に吸着したりすると考えられる。ここでいうアルコール類は、多価アルコールと理解されてもよい。以下、同様である。 A silica composite can be obtained by surface-treating silica with the alcohols described above. By surface-treating silica with alcohols, it is believed that the hydroxyl groups of the alcohols bond with the silanol groups on the silica surface, or the alcohols adsorb to the silica surface. The alcohols referred to here may be understood as polyhydric alcohols. The same applies hereinafter.
　そのようなシリカ複合体の表面では、アルコール類由来のアルキル基等の疎水基と、アルコール類由来の水酸基、シリカ表面のシラノール基等の親水基とが、適度に配置すると考えられる。そのような表面は、塗料、インク、又は、樹脂フィルム若しくは樹脂シート中に一般的に含まれる樹脂成分との親和性が高いため、シリカ複合体が樹脂組成物中に均一に分散され、シリカ複合体同士の凝集が抑制される。 On the surface of such a silica composite, hydrophobic groups such as alkyl groups derived from alcohols, hydroxyl groups derived from alcohols, and hydrophilic groups such as silanol groups on the silica surface are thought to be appropriately arranged. Such a surface has a high affinity with paint, ink, or a resin component generally contained in a resin film or resin sheet, so that the silica composite is uniformly dispersed in the resin composition, and the silica composite Aggregation between bodies is suppressed.
　その結果、例えばシリカ複合体が塗料又はインクの艶消し剤として添加される場合には、形成された塗膜の表面に均一な凹凸が形成され、滑らかに艶消しされた風合いの良い表面が得られる。また特に、シリカ複合体がインクの艶消し剤として添加される場合には、解像度の高い印刷物を得ることができる。また、例えばシリカが樹脂フィルム又は樹脂シートの、アンチブロッキング剤として添加される場合には、得られる樹脂フィルム又は樹脂シートにフィッシュアイ、ムラ、スジ等が生じにくい。 As a result, for example, when the silica composite is added as a matting agent for paints or inks, uniform unevenness is formed on the surface of the formed coating film, and a smoothly matted surface with a good texture is obtained. be done. In particular, when the silica composite is added as a matting agent for the ink, a printed matter with high resolution can be obtained. Further, for example, when silica is added as an anti-blocking agent for a resin film or resin sheet, fish eyes, unevenness, streaks and the like are less likely to occur in the resulting resin film or resin sheet.
　また、ワックス等で表面処理したシリカ複合体の塗料を二度塗りしたときに上塗りした塗料が撥かれる現象が生じる場合がある。これは、シリカ表面のワックス等の有機物が、より相溶性の良い樹脂成分と馴染んでシリカから遊離する等の要因により、塗膜の表面状態が変化するためと考えられる。 In addition, when a silica composite paint surface-treated with wax or the like is applied twice, a phenomenon may occur in which the topcoat paint is repelled. This is thought to be due to factors such as organic matter such as wax on the surface of the silica blending in with the more compatible resin component and being released from the silica, thereby changing the surface state of the coating film.
　これに対し、上述した特定のアルコール類で表面処理されたシリカ複合体の塗料を二度塗りしても上塗りした塗料は撥かれにくい。 On the other hand, even if the silica composite paint surface-treated with the above-mentioned specific alcohol is applied twice, the overcoated paint is less likely to be repelled.
　以下、シリカ複合体について詳細に説明する。 The silica composite will be described in detail below.
　シリカとしては、塗料の添加剤、インクの添加剤、及び樹脂フィルム又は樹脂シートのアンチブロッキング剤の用途に適することから、多孔質シリカが好ましい。多孔質シリカとしては、湿式法により製造される湿式シリカが挙げられる。湿式シリカとしては、具体的には、沈降シリカ、シリカゲル等が挙げられる。シリカとしては、塗料の添加剤、インクの添加剤、及び、樹脂フィルム又は樹脂シートのアンチブロッキング剤の用途により適することから、シリカゲルが好ましい。 As silica, porous silica is preferable because it is suitable for use as an additive for paints, an additive for ink, and an anti-blocking agent for resin films or resin sheets. Porous silica includes wet silica produced by a wet method. Specific examples of wet silica include precipitated silica and silica gel. As silica, silica gel is preferable because it is more suitable for use as an additive for paints, an additive for ink, and an anti-blocking agent for resin films or resin sheets.
　アルコール類としては、上述のとおり、一価アルコール、多価アルコール、及び多価アルコールの誘導体が挙げられる。 As mentioned above, alcohols include monohydric alcohols, polyhydric alcohols, and derivatives of polyhydric alcohols.
　一価アルコールとしては、例えば、一価の飽和又は不飽和の脂肪族アルコール、一価の芳香族アルコール等が挙げられる。一価アルコールとしては、例えば、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、イソブチルアルコール、ｓ－ブタノール、ｔ－ブタノール、１－ペンタノール、２－ペンタノール、３－メチル－１－ブタノール、１－ヘキサノール、２－ヘキサノール、２－エチル－１－ブタノール、１－オクタノール、２－オクタノール、２－エチル－１－ヘキサノール、シクロヘキサノール、ピナコリルアルコール、ベンジルアルコール、イソペンテニルアルコール、３，３－ジメチルアリルアルコール、クロチルアルコール、β－メタリルアルコール、ソルビルアルコール等が挙げられる。一価アルコールの炭素数としては、１以上１０以下であることが好ましく、１以上４以下であることがより好ましい。 Examples of monohydric alcohols include monohydric saturated or unsaturated aliphatic alcohols, monohydric aromatic alcohols, and the like. Examples of monohydric alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, s-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-methyl-1 -butanol, 1-hexanol, 2-hexanol, 2-ethyl-1-butanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, pinacolyl alcohol, benzyl alcohol, isopentenyl alcohol, 3 , 3-dimethylallyl alcohol, crotyl alcohol, β-methallyl alcohol, sorbyl alcohol and the like. The number of carbon atoms in the monohydric alcohol is preferably 1 or more and 10 or less, more preferably 1 or more and 4 or less.
　多価アルコールとしては、例えば、エチレングリコール、１，４－ブタンジオール、２－メチル－１，３－プロパンジオール、１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、２，２－ジメチルー１，３－プロパンジオール、１，２－ヘキサンジオール、２－メチル－２，４－ペンタンジオール、１，２－シクロヘキサンジオール、１，４－シクロヘキサンジオール、ピナコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、プロピレングリコール、トリプロピレングリコール、グリセロール、ジグリセロール、トリグリセロール、トリメチロールエタン、トリメチロールプロパン、ペンタエリトリトール、ジペンタエリトリトール、トリペンタエリトリトール、ソルビトール、スクロース等が挙げられる。多価アルコールの炭素数としては、２以上１０以下であることが好ましく、３以上７以下であることがより好ましい。 Examples of polyhydric alcohols include ethylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2 -dimethyl-1,3-propanediol, 1,2-hexanediol, 2-methyl-2,4-pentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, pinacol, diethylene glycol, triethylene glycol, tetra Ethylene glycol, propylene glycol, tripropylene glycol, glycerol, diglycerol, triglycerol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, sucrose and the like. The number of carbon atoms in the polyhydric alcohol is preferably 2 or more and 10 or less, more preferably 3 or more and 7 or less.
　多価アルコールの誘導体としては、例えば、多価アルコールの水酸基の一部がアルキルエーテル化された化合物等が挙げられる。多価アルコールの誘導体としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノフェニルエーテル、カルビトール、エチルカルビトール、ブチルカルビトール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル等が挙げられる。 Derivatives of polyhydric alcohols include, for example, compounds in which a portion of the hydroxyl groups of polyhydric alcohols are alkyl-etherified. Examples of polyhydric alcohol derivatives include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, carbitol, and ethyl carbitol. , butyl carbitol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono Ethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether and the like.
　これらの中でも、アルコール類としては三価アルコールが好ましい。三価アルコールは、一価アルコール又は二価アルコール等と比較して、シリカとの結合又は吸着に関与せずにシリカ複合体の表面に存在する水酸基が多くなると考えられる。その結果、シリカ複合体の表面に存在する疎水基と親水基とのバランスが適度になるため、樹脂組成物中にシリカ複合体がより均一に分散される。三価アルコールの中でも、アルコール類としては、グリセロール、トリメチロールエタン及びトリメチロールプロパンからなる群より選ばれる少なくとも一つが好ましく、トリメチロールエタン及びトリメチロールプロパンからなる群より選ばれる少なくとも一つがより好ましい。 Among these, trihydric alcohol is preferable as the alcohol. Compared to monohydric alcohols or dihydric alcohols, trihydric alcohols are considered to have more hydroxyl groups present on the surface of the silica composite without participating in bonding or adsorption with silica. As a result, the balance between the hydrophobic groups and the hydrophilic groups present on the surface of the silica composite becomes appropriate, so that the silica composite is more uniformly dispersed in the resin composition. Among trihydric alcohols, the alcohol is preferably at least one selected from the group consisting of glycerol, trimethylolethane and trimethylolpropane, more preferably at least one selected from the group consisting of trimethylolethane and trimethylolpropane.
　シリカ複合体におけるアルコール類の含有量は、樹脂組成物中にシリカ複合体がより均一に分散されることから、０．１質量％以上であることが好ましく、２質量％以上であることがより好ましい。また、シリカに対するアルコール類の結合量又は吸着量には限度があることから、シリカ複合体におけるアルコール類の含有量は、３０質量％以下であることが好ましく、１５質量％以下であることがより好ましい。 The content of the alcohol in the silica composite is preferably 0.1% by mass or more, more preferably 2% by mass or more, because the silica composite is more uniformly dispersed in the resin composition. preferable. In addition, since the amount of binding or adsorption of alcohols to silica is limited, the content of alcohols in the silica composite is preferably 30% by mass or less, more preferably 15% by mass or less. preferable.
　シリカ複合体において、窒素ガス吸着法により求められるＢＥＴ比表面積に対する、水蒸気吸着法により求められるＢＥＴ比表面積の割合は、１５％以上４５％以下であることが好ましく、２５％以上４２％以下であることがより好ましく、２５％以上４０％以下であることが更に好ましい。当該割合は、測定物質の親水性／疎水性の度合いを表す指標であり、値が大きいほど親水性が高い。以下、当該割合を、「親水表面割合」と称する。シリカ複合体では、シリカ表面のシラノール基、アルコール類由来の水酸基、アルコール誘導体由来のエーテル結合等が多いほど、親水表面割合の値が大きくなる。親水表面割合が上述した範囲であると、シリカ複合体の表面の親水性／疎水性の度合いが適度となるため、樹脂組成物中にシリカ複合体がより均一に分散される。 In the silica composite, the ratio of the BET specific surface area obtained by the water vapor adsorption method to the BET specific surface area obtained by the nitrogen gas adsorption method is preferably 15% or more and 45% or less, and is 25% or more and 42% or less. is more preferably 25% or more and 40% or less. The ratio is an index representing the degree of hydrophilicity/hydrophobicity of the substance to be measured, and the greater the value, the higher the hydrophilicity. Hereinafter, this ratio is referred to as "hydrophilic surface ratio". In the silica composite, the greater the number of silanol groups, alcohol-derived hydroxyl groups, alcohol derivative-derived ether bonds, etc. on the silica surface, the greater the value of the hydrophilic surface ratio. When the hydrophilic surface ratio is within the range described above, the degree of hydrophilicity/hydrophobicity of the surface of the silica composite becomes appropriate, so that the silica composite is more uniformly dispersed in the resin composition.
　シリカ複合体において、窒素ガス吸着法により求められるＢＥＴ比表面積は、５０ｍ2／ｇ以上８００ｍ2／ｇ以下であることが好ましく、１００ｍ2／ｇ以上５５０ｍ2／ｇ以下であることがより好ましく、２００ｍ2／ｇ以上３５０以下ｍ2／ｇ以下であることが更に好ましい。このような範囲のＢＥＴ比表面積を有するシリカ複合体は、塗料の添加剤、インクの添加剤、及び樹脂フィルム又は樹脂シートのアンチブロッキング剤の用途に適する。 In the silica composite, the BET specific surface area determined by the nitrogen gas adsorption method is preferably 50 m/g or more and 800 m/g or less, more preferably 100 m/g or more and 550 m/g or less, and 200 m/g or more. It is more preferably 350 or less m<2>/g. A silica composite having a BET specific surface area within such a range is suitable for use as an additive for paints, an additive for inks, and an anti-blocking agent for resin films or resin sheets.
　また、シリカ複合体の細孔容積は、０．３ｃｍ3／ｇ以上２．２ｃｍ3／ｇ以下であることが好ましく、０．５ｃｍ3／ｇ以上２．０ｃｍ3／ｇ以下であることがより好ましい。ここでいう細孔容積は、窒素ガス吸着等温線において相対圧０．９９における窒素ガスの吸着量を液体換算した値である。 The pore volume of the silica composite is preferably 0.3 cm3/g or more and 2.2 cm3/g or less, more preferably 0.5 cm3/g or more and 2.0 cm3/g or less. The pore volume referred to here is a value obtained by liquid-converting the amount of nitrogen gas adsorbed at a relative pressure of 0.99 on the nitrogen gas adsorption isotherm.
　また、シリカ複合体の平均細孔径は、２ｎｍ以上７５ｎｍ以下であることが好ましく、５ｎｍ以上３０ｎｍ以下であることがより好ましい。平均細孔径は、上述した細孔容積と上述した窒素ガス吸着法により求められるＢＥＴ比表面積とから算出することができる。 In addition, the average pore size of the silica composite is preferably 2 nm or more and 75 nm or less, more preferably 5 nm or more and 30 nm or less. The average pore diameter can be calculated from the pore volume described above and the BET specific surface area determined by the nitrogen gas adsorption method described above.
　シリカ複合体の体積平均粒子径は、０．５μｍ以上２０μｍ以下であることが好ましく、１μｍ以上１５μｍ以下であることがより好ましく、２μｍ以上８μｍ以下であることが更に好ましい。体積平均粒子径がこのような範囲であると、例えば、塗膜、インク膜、又は、樹脂フィルム若しくは樹脂シートの表面に、適切なサイズの凹凸を形成できる。一般的に、このような体積平均粒子径の比較的小さいシリカでは凝集が発生しやすくなるが、上述したアルコール類でシリカを表面処理することにより凝集を抑制することができる。なお、ここでいう体積平均粒子径は、水溶液中でレーザー回折散乱法粒子径分布測定装置を用いて測定した値である。 The volume average particle size of the silica composite is preferably 0.5 µm or more and 20 µm or less, more preferably 1 µm or more and 15 µm or less, and even more preferably 2 µm or more and 8 µm or less. When the volume average particle diameter is within such a range, for example, irregularities of an appropriate size can be formed on the surface of a coating film, an ink film, or a resin film or resin sheet. In general, such silica having a relatively small volume-average particle size tends to aggregate, but aggregation can be suppressed by surface-treating the silica with the alcohols described above. The volume average particle size referred to here is a value measured in an aqueous solution using a laser diffraction scattering particle size distribution analyzer.
　シリカ複合体の製造方法は特に限定されない。例えば、シリカと、アルコール類を含む溶液とを混合して得たペースト状の混合物を、乾燥し、微粉化することにより、シリカ複合体を得ることができる。また例えば、湿式法の工程中でシリカのスラリー液に所定量のアルコール類をあらかじめ添加しておき、得られた混合スラリー液を噴霧乾燥してシリカ複合体を得てもよい。また例えば、湿式法で得られたシリカのスラリー液とアルコール類とを高速流動ミキサー等を用いて混合し、混合物を乾燥し、微粉化してシリカ複合体を得てもよい。 The method for producing the silica composite is not particularly limited. For example, a silica composite can be obtained by drying and pulverizing a pasty mixture obtained by mixing silica and a solution containing alcohols. Alternatively, for example, a predetermined amount of alcohol may be added in advance to the silica slurry liquid during the wet process, and the obtained mixed slurry liquid may be spray-dried to obtain the silica composite. Further, for example, a slurry of silica obtained by a wet method and an alcohol may be mixed using a high-speed fluid mixer or the like, and the mixture may be dried and pulverized to obtain a silica composite.
　シリカに対するアルコール類の使用量は、シリカ１００質量部に対して、０．５質量部以上であることが好ましく、２．０質量部以上であることがより好ましい。アルコール類の使用量がシリカ１００質量部に対して、０．５質量部以上であると、樹脂組成物中にシリカ複合体がより均一に分散される。また、シリカに対するアルコール類の使用量は、シリカ１００質量部に対して、１２．０質量部以下であることが好ましく、６．０質量部以下であることがより好ましい。アルコール類の使用量が、シリカ１００質量部に対して１２．０質量部よりも多くても、分散性の向上効果があまり高くならないためである。 The amount of alcohol used relative to silica is preferably 0.5 parts by mass or more, more preferably 2.0 parts by mass or more, relative to 100 parts by mass of silica. When the amount of alcohol used is 0.5 parts by mass or more with respect to 100 parts by mass of silica, the silica composite is more uniformly dispersed in the resin composition. In addition, the amount of alcohol used relative to silica is preferably 12.0 parts by mass or less, more preferably 6.0 parts by mass or less, relative to 100 parts by mass of silica. This is because even if the amount of alcohol used is more than 12.0 parts by mass with respect to 100 parts by mass of silica, the effect of improving dispersibility is not so high.
　シリカ複合体は、上述したとおり、塗料の添加剤、インクの添加剤、又は、樹脂フィルム若しくは樹脂シートのアンチブロッキング剤として好適に使用することができる。ここでいう添加剤とは、塗料又はインク中に何らかの目的で添加されるあらゆるものをいう。例えば、添加剤としては、塗料の場合には、艶消し剤等、インクの場合には、艶消し剤、顔料等が挙げられる。 As described above, the silica composite can be suitably used as a paint additive, an ink additive, or an anti-blocking agent for resin films or resin sheets. Additives as used herein refer to all substances added to paints or inks for some purpose. For example, additives include matting agents and the like in the case of paints, and matting agents, pigments and the like in the case of inks.
　＜樹脂組成物＞
　樹脂組成物は、上述したシリカ複合体を含む。樹脂組成物としては、例えば、塗料、インク、樹脂フィルム又は樹脂シート形成用の組成物等が挙げられる。樹脂フィルム又は樹脂シート形成用の組成物とは、樹脂フィルム又は樹脂シートを形成するための原料をいう。樹脂組成物の形状としては、例えば、ペースト状、ペレット状、板状、粒状、液状等が挙げられる。 <Resin composition>
The resin composition contains the silica composite described above. Examples of resin compositions include paints, inks, compositions for forming resin films or resin sheets, and the like. A composition for forming a resin film or a resin sheet refers to a raw material for forming a resin film or a resin sheet. Examples of the shape of the resin composition include paste, pellet, plate, granule, and liquid.
　樹脂組成物中のシリカ複合体の含有量は、シリカ複合体の使用用途、シリカ複合体に求められる物性等を考慮して適宜設定することができる。 The content of the silica composite in the resin composition can be appropriately set in consideration of the intended use of the silica composite, the physical properties required of the silica composite, and the like.
　一例として、樹脂組成物が塗料又はインクである場合におけるシリカ複合体の含有量は、０．５質量％以上であることが好ましく、１質量％以上であることがより好ましい。シリカ複合体の含有量が０．５質量％以上であると、所望の物性、例えば艶消し剤として使用する場合には、所望の艶消し度合いを達成しやすい。また一例として、シリカ複合体の含有量は、２０質量％以下であることが好ましく、１５質量％以下であることがより好ましい。 As an example, when the resin composition is a paint or ink, the content of the silica composite is preferably 0.5% by mass or more, more preferably 1% by mass or more. When the content of the silica composite is 0.5% by mass or more, desired physical properties, for example, when used as a matting agent, a desired degree of matting can be easily achieved. As another example, the content of the silica composite is preferably 20% by mass or less, more preferably 15% by mass or less.
　また、一例として、樹脂組成物が樹脂フィルム又は樹脂シート形成用の組成物である場合におけるシリカ複合体の含有量は、５０ｐｐｍ（０．００５質量％）以上であることが好ましく、１００ｐｐｍ（０．０１質量％）以上であることがより好ましい。シリカ複合体の含有量が５０ｐｐｍ以上であると、アンチブロッキング剤としての効果が得やすい。また一例として、シリカ複合体の含有量は、１０，０００ｐｐｍ（１質量％）以下であることが好ましく、５，０００ｐｐｍ（０．５質量％）以下であることがより好ましい。 Further, as an example, when the resin composition is a composition for forming a resin film or a resin sheet, the content of the silica composite is preferably 50 ppm (0.005% by mass) or more, and is preferably 100 ppm (0.005% by mass) or more. 01% by mass) or more. When the content of the silica composite is 50 ppm or more, the effect as an anti-blocking agent is likely to be obtained. As another example, the content of the silica composite is preferably 10,000 ppm (1% by mass) or less, more preferably 5,000 ppm (0.5% by mass) or less.
　特に、シリカ複合体は、得られる塗膜、インク膜、又は、樹脂フィルム若しくは樹脂シート等の表面特性を改善させる用途、具体的には、塗料の艶消し剤、インクの艶消し剤、又は、樹脂フィルム若しくは樹脂シートのアンチブロッキング剤等として好適に使用することができる。 In particular, the silica composite is used to improve the surface properties of the resulting coating film, ink film, resin film or resin sheet, specifically, a matting agent for paints, a matting agent for inks, or It can be suitably used as an anti-blocking agent for resin films or resin sheets.
　塗料、インク、又は、樹脂フィルム若しくは樹脂シートには、バインダーとなる樹脂成分の他、塗料、インク、又は、樹脂フィルム若しくは樹脂シートに一般的に配合される各種成分が適宜配合されてもよい。塗料又はインクに配合される樹脂成分としては、例えば、アクリル樹脂、セルロース系樹脂、ウレタン樹脂、アルキド樹脂、エポキシ樹脂、メラミン樹脂等が挙げられる。樹脂フィルム又は樹脂シート形成用の組成物に配合される樹脂成分としては、アクリル樹脂、ナイロン樹脂、ＰＥＴ樹脂、ＰＰ樹脂、ＰＥ樹脂等が挙げられる。なお、樹脂フィルム又は樹脂シート形成用の組成物に配合される樹脂成分としては、シリカ複合体との親和性が高いことから、ナイロン樹脂、アクリル樹脂、及びＰＥＴ樹脂からなる群より選ばれる少なくとも一つが好ましい。 The paint, ink, or resin film or resin sheet may appropriately contain various components that are generally incorporated into the paint, ink, resin film, or resin sheet, in addition to the binder resin component. Examples of resin components to be incorporated in paints or inks include acrylic resins, cellulose resins, urethane resins, alkyd resins, epoxy resins, melamine resins, and the like. Examples of the resin component to be blended in the composition for forming the resin film or resin sheet include acrylic resin, nylon resin, PET resin, PP resin, PE resin, and the like. In addition, as the resin component to be blended in the composition for forming the resin film or resin sheet, at least one selected from the group consisting of nylon resins, acrylic resins, and PET resins, since it has a high affinity with the silica composite. one is preferred.
　＜樹脂フィルム又は樹脂シート＞
　樹脂フィルム又は樹脂シートは、上述したシリカ複合体を含む。樹脂フィルム又は樹脂シートは、上述した樹脂組成物を用いて製造することができる。樹脂フィルム又は樹脂シートは、単層で構成されていてもよく、他の層を含む複数の層で構成されていてもよい。 <Resin film or resin sheet>
The resin film or resin sheet contains the silica composite described above. A resin film or resin sheet can be produced using the resin composition described above. The resin film or resin sheet may be composed of a single layer, or may be composed of a plurality of layers including other layers.
　以下に、本開示の一態様について実施例を挙げて説明するが、本開示は以下の実施例に限定されるものではない。 An embodiment of the present disclosure will be described below with examples, but the present disclosure is not limited to the following examples.
　（実施例１）
　１．シリカ複合体の調製
　トリメチロールエタン（ＴＭＥ）１質量％水溶液を調製した。トリメチロールエタン１質量％水溶液２０ｇに、シリカゲル（「サイリシア（登録商標）３５０」、富士シリシア化学株式会社製）４ｇを添加し、混合することによりペースト状の混合物を得た。得られた混合物を乾燥機にて１１０度で乾燥させた。得られた乾燥物を微粉化することにより、体積平均粒子径３．９μｍのシリカ・ＴＭＥ複合体を得た。 (Example 1)
1. Preparation of Silica Composite A 1% by weight aqueous solution of trimethylolethane (TME) was prepared. 4 g of silica gel (“Silysia (registered trademark) 350” manufactured by Fuji Silysia Chemical Co., Ltd.) was added to 20 g of a 1% by mass trimethylolethane aqueous solution and mixed to obtain a paste-like mixture. The resulting mixture was dried in a dryer at 110 degrees. A silica/TME composite having a volume average particle size of 3.9 μm was obtained by pulverizing the resulting dried product.
　２．塗料の調製
　アクリル樹脂塗料１００ｇ（エスケー化研株式会社製）、及びシリカ・ＴＭＥ複合体３ｇをボトルに入れ、ホモディスパー（プライミクス株式会社製）により１０００ｒｐｍで５分間攪拌し、脱泡のため１時間静置した。 2. Preparation of paint 100 g of acrylic resin paint (manufactured by SK Kaken Co., Ltd.) and 3 g of silica/TME composite are placed in a bottle, stirred at 1000 rpm for 5 minutes with Homodisper (manufactured by Primix Co., Ltd.), and defoamed for 1 hour. left undisturbed.
　また、回転数を３０００ｒｐｍに変更して調製した塗料も併せて準備した。 In addition, a paint prepared by changing the rotation speed to 3000 rpm was also prepared.
　（実施例２）
　トリメチロールエタン水溶液の濃度を２質量％とした以外は実施例１と同様にして、体積平均粒子径３．９μｍのシリカ・ＴＭＥ複合体及び塗料を得た。 (Example 2)
A silica/TME composite with a volume average particle size of 3.9 μm and a coating material were obtained in the same manner as in Example 1, except that the concentration of the trimethylolethane aqueous solution was 2% by mass.
　（実施例３）
　トリメチロールエタン水溶液の濃度を０．６質量％とした以外は実施例１と同様にして、体積平均粒子径３．９μｍのシリカ・ＴＭＥ複合体及び塗料を得た。 (Example 3)
A silica/TME composite and a paint having a volume average particle size of 3.9 μm were obtained in the same manner as in Example 1, except that the concentration of the trimethylolethane aqueous solution was changed to 0.6% by mass.
　（実施例４）
　トリメチロールエタンの代わりにトリメチロールプロパン（ＴＭＰ）を使用した以外は実施例１と同様にして、体積平均粒子径３．９μｍのシリカ・ＴＭＰ複合体及び塗料を得た。 (Example 4)
A silica/TMP composite with a volume average particle size of 3.9 μm and a paint were obtained in the same manner as in Example 1, except that trimethylolpropane (TMP) was used instead of trimethylolethane.
　（実施例５）
　トリメチロールエタンの代わりにグリセロールを使用した以外は実施例１と同様にして、体積平均粒子径３．９μｍのシリカ・グリセロール複合体及び塗料を得た。 (Example 5)
A silica-glycerol composite with a volume average particle size of 3.9 μm and a paint were obtained in the same manner as in Example 1, except that glycerol was used instead of trimethylolethane.
　（実施例６）
　シリカゲル（「サイリシア（登録商標）３５０」、富士シリシア化学株式会社製）の代わりに、シリカゲル（「サイリシア（登録商標）４４０」、富士シリシア化学株式会社製）を使用した以外は実施例１と同様にして、体積平均粒子径６．２μｍのシリカ・ＴＭＥ複合体及び塗料を得た。 (Example 6)
Same as Example 1 except that silica gel (“Silysia (registered trademark) 440”, manufactured by Fuji Silysia Chemical Co., Ltd.) was used instead of silica gel (“Silysia (registered trademark) 350”, manufactured by Fuji Silysia Chemical Co., Ltd.). Then, a silica/TME composite and a paint having a volume average particle size of 6.2 μm were obtained.
　（比較例１）
　表面処理されていないシリカゲル（「サイリシア（登録商標）３５０」、富士シリシア化学株式会社製）を準備した。塗料は、実施例１と同様に調製した。 (Comparative example 1)
Silica gel (“Sylysia (registered trademark) 350”, manufactured by Fuji Silysia Chemical Co., Ltd.) that has not been surface-treated was prepared. The paint was prepared as in Example 1.
　（比較例２）
　表面処理されていないシリカゲル（「サイリシア（登録商標）４４０」、富士シリシア化学株式会社製）を準備した。塗料は、実施例１と同様に調製した。 (Comparative example 2)
Silica gel (“Sylysia (registered trademark) 440”, manufactured by Fuji Silysia Chemical Co., Ltd.) that has not been surface-treated was prepared. The paint was prepared as in Example 1.
　（比較例３）
　ワックス系の有機物で表面処理されたシリカゲル（「サイリシア（登録商標）４４６」、富士シリシア化学株式会社製）を準備した。塗料は、実施例１と同様に調製した。 (Comparative Example 3)
Silica gel (“Silysia (registered trademark) 446”, manufactured by Fuji Silysia Chemical Co., Ltd.) surface-treated with a wax-based organic substance was prepared. The paint was prepared as in Example 1.
　（比較例４）
　シリル化剤で表面処理されたシリカゲル（「サイロホービック（登録商標）２００」、富士シリシア化学株式会社製）を準備した。塗料は、実施例１と同様に調製した。 (Comparative Example 4)
A silica gel surface-treated with a silylating agent ("Sylophobic (registered trademark) 200", manufactured by Fuji Silysia Chemical Co., Ltd.) was prepared. The paint was prepared as in Example 1.
　（評価）
　以下の評価を行った。評価結果を表１に示す。なお、実施例４～６、及び比較例２～４については、簡略化のため凝集粒子数の評価を行っていない。 (evaluation)
The following evaluations were performed. Table 1 shows the evaluation results. For Examples 4 to 6 and Comparative Examples 2 to 4, the number of aggregated particles was not evaluated for the sake of simplification.
　＜ＢＥＴ比表面積の測定＞
　高精度ガス吸着量測定装置（「ＢＥＬＳＯＲＰ（登録商標）－ｍａｘ」、日本ベル株式会社（現マイクロトラック・ベル株式会社）製）を用いて、液体窒素温度（－１９６℃）における窒素ガス相対圧及び窒素ガス分子の吸着量と、２５℃における水蒸気相対圧及び水蒸気分子の吸着量を測定した。得られた窒素ガス吸着等温線及び水蒸気吸着等温線からＢＥＴプロットを得た。ＢＥＴプロットにおける相対圧０．０５～０．３０の範囲の直線の傾きから、比表面積をそれぞれ算出した。 <Measurement of BET specific surface area>
Nitrogen gas relative pressure at liquid nitrogen temperature (-196 ° C.) using a high-precision gas adsorption amount measuring device ("BELSORP (registered trademark)-max", manufactured by Nippon Bell Co., Ltd. (currently Microtrac Bell Co., Ltd.)) and the adsorption amount of nitrogen gas molecules, and the water vapor relative pressure and the adsorption amount of water vapor molecules at 25°C. A BET plot was obtained from the obtained nitrogen gas adsorption isotherm and water vapor adsorption isotherm. Each specific surface area was calculated from the slope of the straight line in the relative pressure range of 0.05 to 0.30 in the BET plot.
　また、窒素ガス吸着等温線から求めたＢＥＴ比表面積に対する、水蒸気吸着等温線から求めたＢＥＴ比表面積の割合（すなわち、親水表面割合）を算出した。 Also, the ratio of the BET specific surface area obtained from the water vapor adsorption isotherm to the BET specific surface area obtained from the nitrogen gas adsorption isotherm (that is, the hydrophilic surface ratio) was calculated.
　＜凝集粒子数＞
　調整した塗料を、溝の深さが０μｍ以上１００μｍ以下である粒ゲージ（太佑機材株式会社製）に塗布し、４０μｍ以上１００μｍ以下の部分に見られる凝集粒子数をカウントした。 <Number of aggregated particles>
The prepared paint was applied to a grain gauge (manufactured by Taiyu Kizai Co., Ltd.) with a groove depth of 0 μm to 100 μm, and the number of agglomerated particles observed in a portion of 40 μm to 100 μm was counted.
　＜塗膜表面の状態＞
　調製した塗料のそれぞれを、全面黒色の隠蔽率測定紙上に４ｍｉｌのアプリケータで塗布し、塗膜の表面を標準光源下で目視観察することにより、塗膜の滑らかさを評価した。評価基準は以下であった。 <Condition of coating film surface>
Each of the prepared paints was applied with a 4-mil applicator onto black hiding rate measuring paper, and the smoothness of the coating film was evaluated by visually observing the surface of the coating film under a standard light source. The evaluation criteria were as follows.
　Ａ：均一で細かい凹凸が形成され、滑らかな表面である。 A: It has a smooth surface with uniform and fine unevenness.
　Ｂ：やや大きい凹凸が少し見られるものの、概ね均一で細かい凹凸が形成され、概ね滑らかな表面である。 B: Although slightly large unevenness is observed, generally uniform and fine unevenness is formed, and the surface is generally smooth.
　Ｃ：細かい凹凸と共にやや大きい凹凸が見られ、滑らかさがあまり十分でない。 C: Slightly large irregularities are seen together with fine irregularities, and the smoothness is not very sufficient.
　Ｄ：細かい凹凸と共にやや大きい凹凸が多く見られ、滑らかさが十分でない。 D: Many fine unevennesses and slightly large unevennesses are observed, and the smoothness is not sufficient.
Figure JPOXMLDOC01-appb-T000001
   　 
　（考察）
　実施例１～６で得られた塗料は、塗膜として仕上げた場合に塗膜表面の滑らかさに優れ、艶消し性能及び風合いに優れていた。
Figure JPOXMLDOC01-appb-T000001
(Discussion)
The paints obtained in Examples 1 to 6 were excellent in the smoothness of the coating film surface when finished as a coating film, and were excellent in matte performance and texture.
　一方、比較例１～４で得られた塗料は、特に回転数を１０００ｒｐｍにして調製した場合に、塗膜表面にシリカの凝集に起因する不均一な凹凸が見られた。 On the other hand, in the paints obtained in Comparative Examples 1 to 4, non-uniform irregularities due to aggregation of silica were observed on the surface of the paint film, especially when the rotation speed was set to 1000 rpm.
　また、実施例１～３を比較すると、実施例３よりも実施例１が優れており、実施例２が塗膜表面の滑らかさにおいて更に優れていた。
  Further, when Examples 1 to 3 were compared, Example 1 was superior to Example 3, and Example 2 was further superior in the smoothness of the coating film surface.

Claims (10)

  1. 　シリカと、前記シリカに結合又は吸着した、多価アルコールと、を有する、塗料の添加剤用、インクの添加剤用、又は、樹脂フィルム若しくは樹脂シートのアンチブロッキング剤用のシリカ複合体。 A silica composite containing silica and a polyhydric alcohol bound or adsorbed to the silica, which is used as an additive for paints, an additive for inks, or an anti-blocking agent for resin films or sheets.
  2. 　前記多価アルコールは三価アルコールを含む、請求項１に記載のシリカ複合体。 The silica composite according to claim 1, wherein the polyhydric alcohol includes trihydric alcohol.
  3. 　前記多価アルコールは、グリセロール、トリメチロールエタン、及びトリメチロールプロパンからなる群より選ばれる少なくとも一つを含む、請求項１又は２に記載のシリカ複合体。 The silica composite according to claim 1 or 2, wherein the polyhydric alcohol contains at least one selected from the group consisting of glycerol, trimethylolethane, and trimethylolpropane.
  4. 　前記多価アルコールは、トリメチロールエタン、及びトリメチロールプロパンからなる群より選ばれる少なくとも一つを含む、請求項１～３のいずれか１項に記載のシリカ複合体。 The silica composite according to any one of claims 1 to 3, wherein the polyhydric alcohol contains at least one selected from the group consisting of trimethylolethane and trimethylolpropane.
  5. 　前記シリカ複合体における前記多価アルコールの含有量が、０．１質量％以上３０質量％以下である、請求項１～請求項４のいずれか１項に記載のシリカ複合体。 The silica composite according to any one of claims 1 to 4, wherein the content of the polyhydric alcohol in the silica composite is 0.1% by mass or more and 30% by mass or less.
  6. 　前記シリカ複合体において、窒素ガス吸着法により求められるＢＥＴ比表面積に対する、水蒸気吸着法により求められるＢＥＴ比表面積の割合が、１５％以上４５％以下である、請求項１～請求項５のいずれか１項に記載のシリカ複合体。 In the silica composite, the ratio of the BET specific surface area obtained by the water vapor adsorption method to the BET specific surface area obtained by the nitrogen gas adsorption method is 15% or more and 45% or less. 2. The silica composite according to item 1.
  7. 　前記シリカ複合体の体積平均粒子径が、０．５μｍ以上２０μｍ以下である、請求項１～請求項６のいずれか１項に記載のシリカ複合体。 The silica composite according to any one of claims 1 to 6, wherein the silica composite has a volume average particle size of 0.5 µm or more and 20 µm or less.
  8. 　前記シリカは湿式シリカを含む、請求項１～請求項７のいずれか１項に記載のシリカ複合体。 The silica composite according to any one of claims 1 to 7, wherein the silica includes wet silica.
  9. 　請求項１～請求項８のいずれか１項に記載のシリカ複合体を含む樹脂組成物。 A resin composition containing the silica composite according to any one of claims 1 to 8.
  10. 　請求項１～請求項８のいずれか１項に記載の、樹脂フィルム又は樹脂シートのアンチブロッキング剤用のシリカ複合体を含む、樹脂フィルム又は樹脂シート。
          A resin film or resin sheet comprising the silica composite for an anti-blocking agent for a resin film or resin sheet according to any one of claims 1 to 8.
PCT/JP2022/000507 2021-01-25 2022-01-11 Silica composite, resin composition, and resin film or resin sheet WO2022158329A1 (en)

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